EP0210082A1 - Fumes producing castable compositions efficacious in the infra-red range - Google Patents
Fumes producing castable compositions efficacious in the infra-red range Download PDFInfo
- Publication number
- EP0210082A1 EP0210082A1 EP86401123A EP86401123A EP0210082A1 EP 0210082 A1 EP0210082 A1 EP 0210082A1 EP 86401123 A EP86401123 A EP 86401123A EP 86401123 A EP86401123 A EP 86401123A EP 0210082 A1 EP0210082 A1 EP 0210082A1
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- EP
- European Patent Office
- Prior art keywords
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- weight
- pyrotechnic composition
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- compound
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000203 mixture Substances 0.000 title claims abstract description 51
- 239000003517 fume Substances 0.000 title description 2
- 239000000779 smoke Substances 0.000 claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002033 PVDF binder Substances 0.000 claims abstract description 15
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 14
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011777 magnesium Substances 0.000 claims abstract description 11
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 9
- 230000005855 radiation Effects 0.000 claims abstract description 8
- 150000001722 carbon compounds Chemical class 0.000 claims abstract description 7
- 150000002790 naphthalenes Chemical class 0.000 claims abstract description 7
- 230000005540 biological transmission Effects 0.000 claims abstract description 5
- 230000026030 halogenation Effects 0.000 claims abstract description 3
- 238000005658 halogenation reaction Methods 0.000 claims abstract description 3
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000004677 Nylon Substances 0.000 claims 1
- 239000004952 Polyamide Substances 0.000 claims 1
- 229920001778 nylon Polymers 0.000 claims 1
- 229920002647 polyamide Polymers 0.000 claims 1
- 230000009969 flowable effect Effects 0.000 abstract description 2
- 238000002485 combustion reaction Methods 0.000 description 11
- 230000006835 compression Effects 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 235000008429 bread Nutrition 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- CKAPSXZOOQJIBF-UHFFFAOYSA-N hexachlorobenzene Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl CKAPSXZOOQJIBF-UHFFFAOYSA-N 0.000 description 3
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000443 aerosol Substances 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
- C06D3/00—Generation of smoke or mist (chemical part)
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B27/00—Compositions containing a metal, boron, silicon, selenium or tellurium or mixtures, intercompounds or hydrides thereof, and hydrocarbons or halogenated hydrocarbons
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S149/00—Explosive and thermic compositions or charges
- Y10S149/11—Particle size of a component
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S149/00—Explosive and thermic compositions or charges
- Y10S149/11—Particle size of a component
- Y10S149/114—Inorganic fuel
Definitions
- the technical sector of the present invention is that of fusible smoke pyrotechnic compositions making it possible to camouflage any target by preventing the transmission of the infrared radiation emitted by it.
- the fuming pyrotechnic compositions based on hexachloroethane (oxidizing agent) and zinc oxide (reducing agent) are well known to those skilled in the art and it will be possible, by way of illustration, to refer to patent US Pat. 779. This kind of composition produces a white screen which is ineffective with respect to infrared sensors working in the windows of transparency of the atmosphere which are 3-5 ⁇ m and 7-14 ⁇ m.
- Patent FR-A-2 560 186 is also known which proposes a pyrotechnic composition intended for the production of opaque smoke with infrared radiation from a target to a thermal sensor, characterized in that it comprises a generating compound, by thermal decomposition of carbon particles whose size is between 1 and 14 ⁇ m, an oxidation-reduction system reacting at a temperature above 1000 ° C and a binder.
- composition can include the following ternary system: - 15 to 25 parts by weight of metal powder, for example magnesium, - 50 to 85 parts by weight of hexachlorobenzene or hexachlorethane (oxidant), - 0 to 30 parts of naphthalene (carbon generator).
- the smoke-producing compositions are most of the time powdery mixtures used by compression. These materials do not always have optimal mechanical properties, are difficult to machine for low compression ratios and are produced individually. Manufacturing requires heavy means such as mixers, mixers, dryers, presses which prohibit the manufacture of large products.
- the manufacturing diagram is complex and the unit price high.
- smoke-producing pyrotechnic compositions intended for the production of a smoke screen preventing the transmission of infrared radiation comprise the following components: - a reducing agent (most commonly magnesium powder) - an oxidant (hexachloroethane or hexachlorobenzene) - a carbon generating binder (naphthalene, anthracene) - a fluorinated binder (Polyvinylidene fluoride).
- a reducing agent most commonly magnesium powder
- an oxidant hexachloroethane or hexachlorobenzene
- carbon generating binder naphthalene, anthracene
- fluorinated binder Polyvinylidene fluoride
- compositions have two drawbacks: - for reasons of toxicity, hexachlorobenzene is no longer commercially available on European markets, - In addition to the problems of industrial implementation mentioned above, they require the mixture of at least four components.
- the object of the present invention is to provide a pyrotechnic composition producing a screen made up of carbon particles to make a target undetectable by a receiver or a missile sensor, but which can be produced by simple casting.
- the subject of the invention is therefore a flowable pyrotechnic composition intended for the production of opaque smoke to prevent the transmission of infrared radiation from a target to a sensor, of the type comprising a general compound.
- carbon particle generator whose dimensions are between 1 and 14 ⁇ m, characterized in that it comprises a halogenated condensed carbon compound fusible between 75 and 120 ° C whose halogenation rate is greater than 3, a chlorinated carbon compound and a metallic powder, reacting together at a temperature of the order of 1500 ° C.
- the carbon compound can be represented by chlorinated naphthalene, the fluorinated compound by polyvinylidene fluoride and the metal powder by magnesium.
- the composition may contain 50 to 90 parts by weight of carbonaceous compound, 8 to 10 parts by weight of polyvinylidene fluoride and 15 to 25 parts by weight of metal powder.
- the pyrotechnic composition according to the invention meets the following three criteria: - a high combustion regime, - an oxygenated combustion medium, - the presence in the composition of a compound with condensed nuclei.
- the condensed nuclei can advantageously carry halogen atoms (fluorine, chlorine) and / or have the greatest possible number of carbon atoms / number of hydrogen atoms. We then take advantage of the presence of these condensed nuclei, associated with the first two criteria, to generate carbon forming a screen of particles with a broad spectrum. Indeed, the presence of oxygen as well as an unfavorable C / H ratio would cause the formation of gaseous molecules (CO2 and H2O) transparent in the visible and the infrared.
- halogen atoms fluorine, chlorine
- the oxidant is then chlorine or fluorine, carried by another molecule, acid generator which, by condensing on atmospheric water vapor, forms an aerosol of solid particles, effective in the spectrum visible against the sensors.
- the oxidizing compound generating carbon particles can be an industrial chlorinated naphthalene called clonacire whose chlorine substitution rate varies between 3.4, and 3.6.
- clonacire 90 and clonacire 115 Two clonacires are marketed: clonacire 90 and clonacire 115, the melting points of which are 90 and 115 ° C respectively.
- the size of the carbon particles is between 1 and 14 ⁇ m.
- An advantage of the pyrotechnic composition and of the smoke ammunition according to the invention lies in the fact that the cloud of opaque infrared smoke consists of fine carbon particles chemically generated homogeneously with a sufficient flow rate.
- Another advantage lies in the fact that it is possible to master the essential factors: the combustion speed of the composition, which makes it possible to obtain a sufficient mass flow rate, - the combustion temperature which must be high and which conditions the good particle size distribution of the carbon particles;
- compositions are pourable or extrudable.
- a family of fusible compositions between 75 and 120 ° C.
- a double objective is achieved: economic by improving production costs, and technological by filling in complicated geometric shapes.
- These compositions lend themselves better to modern industrialization and their interests are obvious: - suppression of compression as a means of implementation (these compositions can however be implemented by compression), - the possibility of pouring large-diameter breads to supply generators intended for area defense, which is impossible with compressed compositions, - optimal density, - good machinability, - good impact resistance.
- Another advantage is that it is possible to incorporate fibers of chemical origin with a carbon skeleton, the pyrolysis of which at high temperature will generate opacifying carbon particles.
- the overall composition can be obtained by mixing only 3 components: reducing agent - chlorinated naphthalene - polyvinylidene fluoride.
- the metal powder is first subjected to a steaming at approximately 50 ° C for 24 hours.
- the fusible carbon compound is then introduced into the reactor and the mixture is heated with stirring to a temperature 15 ° C higher than the melting level.
- the polyvinylidene fluoride and the reducing agent are then successively added and the melting temperature is maintained for ten minutes with stirring to homogenize the mixture well.
- the casting can then take place.
- the breads obtained are then taken up by machining in order to eliminate shrinkage.
- the combustion speed is measured on a cylindrical test tube 3cm long and 3cm in diameter produced by compression of 6.107 Pa.
- the occulting power is measured using two thermal cameras working in the bands 3-5 and 8-12 um arranged 4.5 m from an emitter constituted by an extended source of 20 cm of coast increased to 200 ° C in a tunnel.
- the obscuring power of the smoke can be defined as the time during which the image of the extended source is partially or completely erased by the passage of this smoke between the camera and the extended source.
- the absorption coefficient A ⁇ (m ⁇ 1) is measured on two bands of wavelength from 7.65 to 13.2 ⁇ m and from 3.3 to 4.2 ⁇ m by application of Beer's law.
- compositions are produced by way of examples in the form of breads according to the preceding indications which are tested as specified above, at the same time as a reference composition described according to Example I of the FR-A patent. -2 560 186.
- compositions 1 and 2 are not sensitive to cracking. Similar results are obtained with compositions 3 and 4.
- the blackout power results from the color processing of a thermal image and is expressed in seconds.
- the absorption coefficient A ⁇ obtained thanks to the spectroradiometer, reflects the capacity of smoke to obscure for a very short time but is not representative of the anti-infrared power over time.
- composition 4 has excellent anti-infrared capacities. Its optimal density and low combustion speed make it suitable for producing large caliber smoke greater than 120 mm.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Botany (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Aiming, Guidance, Guns With A Light Source, Armor, Camouflage, And Targets (AREA)
- Air Bags (AREA)
Abstract
L'invention concerne une composition pyrotechnique coulable destinée à la production de fumée opaque pour interdire la transmission du rayonnement infrarouge d'une cible vers un capteur, du type comportant un composé générateur de particules de carbone dont les dimensions sont comprises entre 1 et 14 µm.The invention relates to a flowable pyrotechnic composition intended for the production of opaque smoke to prevent the transmission of infrared radiation from a target to a sensor, of the type comprising a compound generating carbon particles whose dimensions are between 1 and 14 μm. .
Elle comprend un composé carboné condensé halogéné fusible entre 75 et 120°C dont le taux d'halogénation est supérieur à 3, tel le naphtalène chloré, un composé carboné fluoré, tel le polyfluorure de vinylidène, et une poudre métallique, tel le magnésium, réagissant ensemble à une température de l'ordre de 1500°C.It comprises a halogenated condensed carbon compound fusible between 75 and 120 ° C. whose halogenation rate is greater than 3, such as chlorinated naphthalene, a fluorinated carbon compound, such as polyvinylidene fluoride, and a metallic powder, such as magnesium, reacting together at a temperature of the order of 1500 ° C.
Application au camouflage de cibles émettant un rayonnement infrarouge. Application to camouflage targets emitting infrared radiation.
Description
Le secteur technique de la présente invention est celui des compositions pyrotechniques fumigènes fusibles permettant de camoufler une cible quelconque en empêchant la transmission du rayonnement infrarouge émis par celle-ci.The technical sector of the present invention is that of fusible smoke pyrotechnic compositions making it possible to camouflage any target by preventing the transmission of the infrared radiation emitted by it.
Il existe actuellement peu de publications relatives à la production d'un écran de fumée obscurcissant, à large spectre, c'est-à-dire efficace dans tout le domaine du visible et jusqu'à l'infrarouge lointain de 0,4 à 14 µm.There are currently few publications relating to the production of a broad-spectrum obscuring smoke screen, that is to say effective in the entire visible range and up to the far infrared from 0.4 to 14 µm.
Les compositions pyrotechniques fumigènes à base d'hexachloréthane (oxydant) et d'oxyde de zinc (réducteur) sont bien connues de l'homme de l'art et on pourra à titre d'illustration se référer au brevet US-A-2 939 779. Ce genre de composition produit un écran blanc inefficace vis-à-vis des capteurs infrarouges travaillant dans les fenêtres de transparence de l'atmosphère qui sont 3-5 µm et 7-14 µm.The fuming pyrotechnic compositions based on hexachloroethane (oxidizing agent) and zinc oxide (reducing agent) are well known to those skilled in the art and it will be possible, by way of illustration, to refer to patent US Pat. 779. This kind of composition produces a white screen which is ineffective with respect to infrared sensors working in the windows of transparency of the atmosphere which are 3-5 µm and 7-14 µm.
L'utilisation d'un aérosol composé de fines gouttelettes ou de particules solides a déjà été proposé pour arrêter le rayonnement infrarouge ; toutefois, les écrans formés sont très sensibles aux conditions atmosphériques (vent et humidité relative dans le cas des chlorures métalliques) et l'efficacité est peu durable. A titre indicatif, on pourra se reporter aux brevets FR-A-2 299 617 et 2 309 828.The use of an aerosol composed of fine droplets or solid particles has already been proposed to stop infrared radiation; however, the screens formed are very sensitive to atmospheric conditions (wind and relative humidity in the case of metal chlorides) and the effectiveness is not long-lasting. As an indication, reference may be made to patents FR-A-2 299 617 and 2 309 828.
On connaît également le brevet FR-A-2 560 186 qui propose une composition pyrotechnique destinée à la production d'une fumée opaque aux rayonnements infrarouges d'une cible vers un capteur thermique, caractérisée en ce qu'elle comprend un composé générateur, par décomposition thermique, de particules de carbone dont la dimension est comprise entre 1 et 14 µm, un système oxydo-réducteur réagissant à une température supérieure à 1000°C et un liant.Patent FR-A-2 560 186 is also known which proposes a pyrotechnic composition intended for the production of opaque smoke with infrared radiation from a target to a thermal sensor, characterized in that it comprises a generating compound, by thermal decomposition of carbon particles whose size is between 1 and 14 µm, an oxidation-reduction system reacting at a temperature above 1000 ° C and a binder.
Ce type de compositions peut comprendre le système ternaire suivant :
- 15 à 25 parties en poids de poudre métallique, par exemple le magnésium,
- 50 à 85 parties en poids d'hexachlorobenzène ou d'hexachloréthane (oxydant),
- 0 à 30 parties de naphtalène (générateur de carbone).This type of composition can include the following ternary system:
- 15 to 25 parts by weight of metal powder, for example magnesium,
- 50 to 85 parts by weight of hexachlorobenzene or hexachlorethane (oxidant),
- 0 to 30 parts of naphthalene (carbon generator).
Si l'on excepte le phosphore qui est coulé au moment de sa mise en oeuvre, mais est inefficace dans l'infrarouge, les compositions fumigènes sont la plupart du temps des mélanges pulvérulents mis en oeuvre par compression. Ces matériaux ne présentent pas toujours des propriétés mécaniques optimales, sont difficilement usinables pour de faibles taux de compression et sont fabriqués unitairement. La fabrication exige des moyens lourds tels que malaxeurs, mélangeurs, séchoirs, presses qui interdisent la fabrication de produits de grandes dimensions. Le synoptique de fabrication est complexe et le prix unitaire élevé.With the exception of phosphorus which is poured at the time of its implementation, but is ineffective in the infrared, the smoke-producing compositions are most of the time powdery mixtures used by compression. These materials do not always have optimal mechanical properties, are difficult to machine for low compression ratios and are produced individually. Manufacturing requires heavy means such as mixers, mixers, dryers, presses which prohibit the manufacture of large products. The manufacturing diagram is complex and the unit price high.
De plus, les compositions pyrotechniques fumigènes destinées à la production d'un écran de fumée interdisant la transmission du rayonnement infrarouge comportent les composants suivants :
- un réducteur (poudre de magnésium le plus généralement)
- un oxydant (hexachloroéthane ou hexachlorobenzène)
- un liant générateur de carbone (naphtalène, anthracène)
- un liant fluoré (Polyfluorure de vinylidène).In addition, smoke-producing pyrotechnic compositions intended for the production of a smoke screen preventing the transmission of infrared radiation comprise the following components:
- a reducing agent (most commonly magnesium powder)
- an oxidant (hexachloroethane or hexachlorobenzene)
- a carbon generating binder (naphthalene, anthracene)
- a fluorinated binder (Polyvinylidene fluoride).
Ces compositions présentent deux inconvénients :
- l'hexachlorobenzène n'est plus, pour des raisons de toxicité, commercialement disponible sur les marchés européens,
- outre les problèmes de mise en oeuvre industrielle mentionées ci-avant, elles nécessitent le mélange d'au moins quatre composants.These compositions have two drawbacks:
- for reasons of toxicity, hexachlorobenzene is no longer commercially available on European markets,
- In addition to the problems of industrial implementation mentioned above, they require the mixture of at least four components.
Le but de la présente invention est de fournir une composition pyrotechnique produisant un écran constitué de particules de carbone pour rendre indétectable une cible par un récepteur ou un capteur de missile, mais qui peut être réalisée par simple coulée.The object of the present invention is to provide a pyrotechnic composition producing a screen made up of carbon particles to make a target undetectable by a receiver or a missile sensor, but which can be produced by simple casting.
L'invention a donc pour objet une composition pyrotechnique coulable destinée à la production de fumée opaque pour interdire la transmission du rayonnement infrarouge d'une cible vers un capteur, du type comportant un composé gé nérateur de particules de carbone dont les dimensions sont comprises entre 1 et 14 µm, caractérisée en ce qu'elle comprend un composé carboné condensé halogéné fusible entre 75 et 120°C dont le taux d'halogénation est supérieur à 3, un composé carboné chloré et une poudre métallique, réagissant ensemble à une température de l'ordre de 1500°C.The subject of the invention is therefore a flowable pyrotechnic composition intended for the production of opaque smoke to prevent the transmission of infrared radiation from a target to a sensor, of the type comprising a general compound. carbon particle generator whose dimensions are between 1 and 14 µm, characterized in that it comprises a halogenated condensed carbon compound fusible between 75 and 120 ° C whose halogenation rate is greater than 3, a chlorinated carbon compound and a metallic powder, reacting together at a temperature of the order of 1500 ° C.
Avantageusement, le composé carboné peut être représenté par le naphtalène chloré, le composé fluoré par le polyfluorure de vinylidène et la poudre métallique par le magnésium.Advantageously, the carbon compound can be represented by chlorinated naphthalene, the fluorinated compound by polyvinylidene fluoride and the metal powder by magnesium.
La composition peut renfermer 50 à 90 parties en poids de composé carboné, 8 à 10 parties en poids de polyfluorure de vinylidène et 15 à 25 parties en poids de poudre métallique.The composition may contain 50 to 90 parts by weight of carbonaceous compound, 8 to 10 parts by weight of polyvinylidene fluoride and 15 to 25 parts by weight of metal powder.
La composition pyrotechnique selon l'invention répond aux trois critères suivants :
- un régime de combustion élevé,
- un milieu de combustion sous-oxygéné,
- la présence dans la composition d'un composé à noyaux condensés.The pyrotechnic composition according to the invention meets the following three criteria:
- a high combustion regime,
- an oxygenated combustion medium,
- the presence in the composition of a compound with condensed nuclei.
Les noyaux condensés peuvent être, avantageusement, porteurs d'atomes d'halogènes (fluor, chlore) et/ou présenter un rapport nombre d'atomes de carbone/nombre d'atomes d'hydrogène le plus grand possible. On profite alors de la présence de ces noyaux condensés, associée aux deux premiers critères, pour générer du carbone formant un écran de particules à large spectre. En effet, la présence d'oxygène ainsi qu'un rapport C/H défavorable provoqueraient la formation de molécules gazeuses (CO₂ et H₂O) transparentes dans le visible et l'infrarouge.The condensed nuclei can advantageously carry halogen atoms (fluorine, chlorine) and / or have the greatest possible number of carbon atoms / number of hydrogen atoms. We then take advantage of the presence of these condensed nuclei, associated with the first two criteria, to generate carbon forming a screen of particles with a broad spectrum. Indeed, the presence of oxygen as well as an unfavorable C / H ratio would cause the formation of gaseous molecules (CO₂ and H₂O) transparent in the visible and the infrared.
Dans la composition pyrotechnique, l'oxydant est alors le chlore ou le fluor, porté par une autre molécule, générateur d'acide qui, en se condensant sur la vapeur d'eau atmosphérique, forme un aérosol de particules solides, efficace dans le spectre visible contre les capteurs.In the pyrotechnic composition, the oxidant is then chlorine or fluorine, carried by another molecule, acid generator which, by condensing on atmospheric water vapor, forms an aerosol of solid particles, effective in the spectrum visible against the sensors.
Le composé oxydant générateur de particules de carbone peut être un naphtalène chloré industriel appelé clonacire dont le taux de substitution en chlore varie entre 3,4, et 3,6. Deux clonacires sont commercialisées : la clonacire 90 et la clonacire 115 dont les points de fusion sont respectivement 90 et 115°C. La dimension des particules de carbone est comprise entre 1 et 14 µm.The oxidizing compound generating carbon particles can be an industrial chlorinated naphthalene called clonacire whose chlorine substitution rate varies between 3.4, and 3.6. Two clonacires are marketed: clonacire 90 and clonacire 115, the melting points of which are 90 and 115 ° C respectively. The size of the carbon particles is between 1 and 14 µm.
Un avantage de la composition pyrotechnique et de la munition fumigène selon l'invention réside dans le fait que le nuage de fumée opaque à l'infrarouge est constitué de fines particules de carbone générées par voie chimique de façon homogène avec un débit suffisant.An advantage of the pyrotechnic composition and of the smoke ammunition according to the invention lies in the fact that the cloud of opaque infrared smoke consists of fine carbon particles chemically generated homogeneously with a sufficient flow rate.
Un autre avantage réside dans le fait qu'il est possible de maitriser les facteurs essentiels :
- la vitesse de combustion de la composition, ce qui permet d'obtenir un débit massique suffisant,
- la température de combustion qui doit être élevée et qui conditionne la bonne répartition granulométrique des particules de carbone;Another advantage lies in the fact that it is possible to master the essential factors:
the combustion speed of the composition, which makes it possible to obtain a sufficient mass flow rate,
- the combustion temperature which must be high and which conditions the good particle size distribution of the carbon particles;
Un autre avantage réside dans le fait que ces compositions sont coulables ou extrudables. En effet, en proposant une famille de compositions fusibles entre 75 et 120°C, on atteint un double objectif : économique par l'amélioration des coûts de revient, et technologique par le remplissage de formes géométriques compliquées. Ces compositions se prêtent mieux à une industrialisation moderne et leurs intérêts sont évidents:
- suppression de la compression comme moyen de mise en oeuvre (ces compositions peuvent toutefois être mises en oeuvre par compression),
- la possibilité de couler des pains de grand diamétre pour alimenter des générateurs destinés à la défense de zone, ce qui est impossible avec des compositions comprimées,
- densité optimale,
- bonne usinabilité,
- bonne tenue au choc.Another advantage lies in the fact that these compositions are pourable or extrudable. In fact, by proposing a family of fusible compositions between 75 and 120 ° C., a double objective is achieved: economic by improving production costs, and technological by filling in complicated geometric shapes. These compositions lend themselves better to modern industrialization and their interests are obvious:
- suppression of compression as a means of implementation (these compositions can however be implemented by compression),
- the possibility of pouring large-diameter breads to supply generators intended for area defense, which is impossible with compressed compositions,
- optimal density,
- good machinability,
- good impact resistance.
Le comportement mécanique de ces compositions est particulièrement intéressant; on constate un fluage sous presse qui empêche une décohésion de la matière. Ceci est dû à la présence des clonacires, produits cireux qui confèrent à ces compositions un comportement visco-élastique que l'on ne retrouve pas dans les compositions décrites dansele brevet FR-A-2 560 186.The mechanical behavior of these compositions is particularly interesting; there is a creep in the press which prevents decohesion of the material. This is due to the presence of clonacires, waxy products which confer on these compositions a visco-elastic behavior which one does not not found in the compositions described in patent FR-A-2,560,186.
Un autre avantage est que l'on peut y incorporer des fibres d'origine chimique à squelette carboné dont la pyrolyse à haute température génèrera des particules de carbone opacifiantes.Another advantage is that it is possible to incorporate fibers of chemical origin with a carbon skeleton, the pyrolysis of which at high temperature will generate opacifying carbon particles.
Enfin, la composition globale peut être obtenue par le mélange de seulement 3 composants :
réducteur - naphtalène chloré - polyfluorure de vinylidène.Finally, the overall composition can be obtained by mixing only 3 components:
reducing agent - chlorinated naphthalene - polyvinylidene fluoride.
Pour préparer les compositions pyrotechniques selon l'invention on s'y prend de la manière suivante :To prepare the pyrotechnic compositions according to the invention, this is done as follows:
La poudre métallique est d'abord soumise à un étuvage à 50°C environ pendant 24 heures.The metal powder is first subjected to a steaming at approximately 50 ° C for 24 hours.
On introduit alors dans le réacteur le composé carboné fusible et on chauffe en agitant jusqu'à une température supérieure de 15°C au palier de fusion. On ajoute alors successivement le polyfluorure de vinylidène et le réducteur et on maintient à la température de fusion pendant une dizaine de minutes en agitant pour bien homogénéiser le mélange. La coulée peut ensuite s'effectuer. Les pains obtenus sont ensuite repris par usinage afin d'éliminer la retassure. Un canal central ayant été ménagé au moment de la coulée, ils sont alors chargeables en artifices.The fusible carbon compound is then introduced into the reactor and the mixture is heated with stirring to a temperature 15 ° C higher than the melting level. The polyvinylidene fluoride and the reducing agent are then successively added and the melting temperature is maintained for ten minutes with stirring to homogenize the mixture well. The casting can then take place. The breads obtained are then taken up by machining in order to eliminate shrinkage. A central channel having been provided at the time of casting, they can then be loaded with fireworks.
Pour chacune des compositions indiquées ci-après, on a mesuré la vitesse de combustion, la tenue mécanique, le pouvoir d'occultation et le coefficient d'absorption.For each of the compositions indicated below, the combustion speed, the mechanical strength, the occulting power and the absorption coefficient were measured.
La vitesse de combustion est mesurée sur une éprouvette cylindrique de 3cm de long et de 3cm de diamètre réalisée par compression de 6.10⁷ Pa.The combustion speed is measured on a cylindrical test tube 3cm long and 3cm in diameter produced by compression of 6.10⁷ Pa.
Le pouvoir d'occultation est mesuré à l'aide de deux caméras thermiques travaillant dans les bandes 3-5 et 8-12 um disposées à 4,5 m d'un émetteur constitué par une source étendue de 20 cm de côte portée à 200°C dans un tunnel. Le pouvoir d'occultation de la fumée peut être défini comme le temps pendant lequel l'image de la source étendue est partiellement ou totalement effacée par le passage de cette fumée entre la caméra et la source étendue.The occulting power is measured using two thermal cameras working in the bands 3-5 and 8-12 um arranged 4.5 m from an emitter constituted by an extended source of 20 cm of coast increased to 200 ° C in a tunnel. The obscuring power of the smoke can be defined as the time during which the image of the extended source is partially or completely erased by the passage of this smoke between the camera and the extended source.
Le coefficient d'absorption AΔλ (m⁻¹) est mesuré sur deux bandes de longueur d'onde de 7,65 à 13,2 µm et de 3,3 à 4,2 µm par application de la loi de Beer.The absorption coefficient AΔλ (m⁻¹) is measured on two bands of wavelength from 7.65 to 13.2 µm and from 3.3 to 4.2 µm by application of Beer's law.
Dans le tableau 1, on a rassemblé les résultats des mesures de vitesse de combustion et de tenue mécanique définies ci-après :
- combustion : on mesure la vitesse de combustion à l'air libre V (1 atm) et la vitesse de combustion sous la pression régant à l'intérieur d'une munition fumigène V (P) prête à l'emploi, c'est-à-dire constituée d'un pot fumigène de 36 cm de long et de 8 cm de diamètre,
- tenue mécanique : on mesure l'effort maximum à la compression Smc (en Pa), l'écrasement emc à cet effort, et le module de young (Ec),
- coefficients de sensibilité à la friction (CsF) et à l'impact (Csi) selon les modes opératoires connus utilisés dans ce domaine technique.In Table 1, the results of the combustion speed and mechanical strength measurements defined below are collated:
- combustion: we measure the combustion speed in the open air V (1 atm) and the combustion speed under the pressure prevailing inside a smoke ammunition V (P) ready for use, this is that is to say made up of a smoke pot 36 cm long and 8 cm in diameter,
- mechanical strength: we measure the maximum force at compression Smc (in Pa), the crushing emc at this force, and the module of young (Ec),
- coefficients of sensitivity to friction (CsF) and to impact (Csi) according to the known operating modes used in this technical field.
On réalise à titre d'exemples les diverses compositions suivantes sous forme de pains selon les indications précédentes que l'on teste comme précisé ci-dessus, en même temps qu'une composition de référence décrite selon l'exemple I du brevet FR-A-2 560 186.The following various compositions are produced by way of examples in the form of breads according to the preceding indications which are tested as specified above, at the same time as a reference composition described according to Example I of the FR-A patent. -2 560 186.
- 25 parties de magnésium,
- 70 parties de clonacire 90,
- 15 parties de polyfluorure de vinylidène.- 25 parts of magnesium,
- 70 parts of clonacire 90,
- 15 parts of polyvinylidene fluoride.
- 25 parties de magnésium,
- 70 parties de clonacire 115,
- 15 parties de polyfluorure de vinylidène.- 25 parts of magnesium,
- 70 parts of clonacire 115,
- 15 parts of polyvinylidene fluoride.
- 25 parties de magnésium,
- 70 parties de clonacire 115,
- 15 parties de polyfluorure de vinylidène,
- 2 parties de fibres de carbone.- 25 parts of magnesium,
- 70 parts of clonacire 115,
- 15 parts of polyvinylidene fluoride,
- 2 parts of carbon fibers.
- 17 parties de magnésium,
- 70 parties de clonacire 115,
- 13 parties de polyfluorure de vinylidène.
- 70 parts of clonacire 115,
- 13 parts of polyvinylidene fluoride.
On observe un fluage sans contrainte qui montre que les compositions 1 et 2 ne sont pas sensibles à la fissuration. On obtient des résultats analogues avec les compositions 3 et 4.An unconstrained creep is observed, which shows that compositions 1 and 2 are not sensitive to cracking. Similar results are obtained with compositions 3 and 4.
Les résultats données ci-après dans les tableaux 3 et 4 sont obtenus dans les mêmes conditions expérimentales, dans un tunnel figurant un écoulement laminaire des fumées générées.
- masse de composition fumigène 1,5 à 1,7 Kg
- diamètre de l'artifice 80 mm
- vent 1,20 m/s
- fumée générée à 21 de l'axe de mesure
- section de la veine de fumée 1 m2
- trajet optique d = 1mThe results given below in Tables 3 and 4 are obtained under the same experimental conditions, in a tunnel showing a laminar flow of the fumes generated.
- mass of smoke composition 1.5 to 1.7 Kg
- diameter of the device 80 mm
- wind 1.20 m / s
- smoke generated at 21 from the measuring axis
- section of the smoke stream 1 m2
- optical path d = 1m
Le pouvoir d'occultation résulte du traitement couleur d'une image thermique et est exprimée en secondes.The blackout power results from the color processing of a thermal image and is expressed in seconds.
C'est le temps pendant lequel l'atténuation du signal est supérieure à un pourcentage dans la bande considérée. Le coefficient d'absorption AΔλ, obtenu grace au spectroradiomètre, traduit la capacité d'une fumée à occulter pendant un temps très court mais n'est pas représentatif du pouvoir anti-infrarouge dans le temps.
On voit que la composition 4 a d'excellentes capacités anti-infrarouge. Sa densité optimale et sa faible vitesse de combustion la rendent apte à la réalisation de fumigène de gros calibre supérieur à 120 mm.It can be seen that composition 4 has excellent anti-infrared capacities. Its optimal density and low combustion speed make it suitable for producing large caliber smoke greater than 120 mm.
Claims (8)
- 25 parties en poids de magnésium,
- 70 parties en poids de naphtalène chloré,
- 15 parties en poids de polyfluorure de vinylidène.4 - Pyrotechnic composition according to claim 3, characterized in that it comprises:
- 25 parts by weight of magnesium,
- 70 parts by weight of chlorinated naphthalene,
- 15 parts by weight of polyvinylidene fluoride.
- 17 parties en poids de magnésium,
- 70 parties en poids de naphtalène chloré,
- 13 parties en poids de polyfluorure de vinylidène.5 - Pyrotechnic composition according to claim 3, characterized in that it comprises:
- 17 parts by weight of magnesium,
- 70 parts by weight of chlorinated naphthalene,
- 13 parts by weight of polyvinylidene fluoride.
- 25 parties en poids de magnésium,
- 70 parties en poids de naphtalène chloré,
- 15 parties en poids de polyfluorure de vinylidène,
- 2 parties en poids de fibres de carbone.8 - Pyrotechnic composition according to claim 7, characterized in that it comprises:
- 25 parts by weight of magnesium,
- 70 parts by weight of chlorinated naphthalene,
- 15 parts by weight of polyvinylidene fluoride,
- 2 parts by weight of carbon fibers.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8508603 | 1985-06-07 | ||
| FR8508603A FR2583037B1 (en) | 1985-06-07 | 1985-06-07 | EFFICIENT FLOWABLE SMOKING COMPOSITIONS IN INFRARED |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0210082A1 true EP0210082A1 (en) | 1987-01-28 |
| EP0210082B1 EP0210082B1 (en) | 1988-08-10 |
Family
ID=9319968
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP86401123A Expired EP0210082B1 (en) | 1985-06-07 | 1986-05-27 | Fumes producing castable compositions efficacious in the infra-red range |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4698108A (en) |
| EP (1) | EP0210082B1 (en) |
| CA (1) | CA1271334A (en) |
| DE (1) | DE3660487D1 (en) |
| FR (1) | FR2583037B1 (en) |
| NO (1) | NO164591C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4337071C1 (en) * | 1993-10-29 | 1995-03-02 | Nico Pyrotechnik | Pyrotechnic smoke charge for camouflage purposes and its use in a smoke body |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2617474B1 (en) * | 1987-07-02 | 1990-01-05 | Lacroix E Tous Artifices | PYROTECHNIC COMPOSITION FOR THE PRODUCTION OF OPAQUE SMOKE WITH INFRARED RADIATION, MANUFACTURING METHOD AND LURE COMPRISING SUCH A COMPOSITION |
| DE3728380C1 (en) * | 1987-08-26 | 1988-11-24 | Nico Pyrotechnik | Pyrotechnic mixture for the production of a camouflage mist and ignition mixture therefor |
| DE4030430C1 (en) * | 1990-09-26 | 1993-12-02 | Buck Chem Tech Werke | Compsn. for generating IR-opaque smoke, esp. for camouflage - contains magnesium@ powder, fluoro:polymer, chloro:paraffin and aromatic cpd., esp. anthracene, phthalic anhydride, 2-benzoyl-pyridine etc. |
| GB9120801D0 (en) * | 1991-10-01 | 1995-03-08 | Secr Defence | Propelled pyrotechnic decoy flare |
| GB9120803D0 (en) * | 1991-10-01 | 1995-03-08 | Secr Defence | Pyrotechnic decoy flare |
| DE4230826C1 (en) * | 1992-09-15 | 1994-03-03 | Buck Chem Tech Werke | Camouflage method for protecting a military object and camouflage particles for its implementation |
| GB2274840B (en) * | 1993-02-05 | 1997-04-09 | Standard Fireworks Ltd | Composition and device incorporating it |
| US5470408A (en) * | 1993-10-22 | 1995-11-28 | Thiokol Corporation | Use of carbon fibrils to enhance burn rate of pyrotechnics and gas generants |
| FR2930984A1 (en) * | 1994-03-15 | 2009-11-13 | Poudres Et Explosifs Snpe Sa S | METHOD AND AMMUNITION OF COUNTER-MEASUREMENT BY UNIDIRECTIONAL VISION SCREEN |
| FR2840978B1 (en) | 2002-06-12 | 2004-09-03 | Giat Ind Sa | MASKING AMMUNITION |
| FR2878320B1 (en) | 2004-11-22 | 2009-05-08 | Giat Ind Sa | AMMUNITION OR COMPONENT OF AMMUNITION COMPRISING A STRUCTURAL ENERGETIC MATERIAL |
| US7343861B1 (en) | 2005-05-31 | 2008-03-18 | The United States Of America As Represented By The Secretary Of The Navy | Device and method for producing an infrared emission at a given wavelength |
| DE102012015761A1 (en) * | 2012-08-09 | 2014-02-13 | Diehl Bgt Defence Gmbh & Co. Kg | Active mass for a pyrotechnic decoy with high emissivity |
| DE102012015762A1 (en) * | 2012-08-09 | 2014-02-13 | Diehl Bgt Defence Gmbh & Co. Kg | High-performance active mass for a pyrotechnic decoy with a fluorinated carbon compound |
| FR3049598B1 (en) | 2016-04-04 | 2020-06-12 | Nexter Munitions | EFFICIENT SMOKING COMPOSITION IN THE VISIBLE AND INFRARED FIELDS |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2054210A1 (en) * | 1969-11-05 | 1971-05-13 | Etat Francais, vertr durch den Mimstre des Armees (Armement), Paris | Luminous fuel |
| DE2451701A1 (en) * | 1974-10-31 | 1976-05-06 | Feistel Pyrotech Fab | Smoke flares contg. high mol. chlorine donor and metal powder - have reduced moisture sensitivity and self ignition tendency |
| US3983816A (en) * | 1974-01-16 | 1976-10-05 | Thiokol Corporation | Compositions for producing flickering signals |
| DE2556256A1 (en) * | 1975-12-13 | 1977-06-16 | Nico Pyrotechnik | Aromatic hydrocarbon modified pyrotechnic smoke compsn. - to produce smoke impenetrable by visible and infrared radiation |
| DE3147850A1 (en) * | 1981-12-03 | 1983-06-09 | Messerschmitt-Bölkow-Blohm GmbH, 8000 München | Wide-band camouflage mist |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1318074A (en) * | 1919-10-07 | Egbert clyde gowdy |
-
1985
- 1985-06-07 FR FR8508603A patent/FR2583037B1/en not_active Expired
-
1986
- 1986-05-13 NO NO861901A patent/NO164591C/en not_active IP Right Cessation
- 1986-05-27 DE DE8686401123T patent/DE3660487D1/en not_active Expired
- 1986-05-27 EP EP86401123A patent/EP0210082B1/en not_active Expired
- 1986-06-03 US US06/869,894 patent/US4698108A/en not_active Expired - Lifetime
- 1986-06-06 CA CA000511019A patent/CA1271334A/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2054210A1 (en) * | 1969-11-05 | 1971-05-13 | Etat Francais, vertr durch den Mimstre des Armees (Armement), Paris | Luminous fuel |
| US3983816A (en) * | 1974-01-16 | 1976-10-05 | Thiokol Corporation | Compositions for producing flickering signals |
| DE2451701A1 (en) * | 1974-10-31 | 1976-05-06 | Feistel Pyrotech Fab | Smoke flares contg. high mol. chlorine donor and metal powder - have reduced moisture sensitivity and self ignition tendency |
| DE2556256A1 (en) * | 1975-12-13 | 1977-06-16 | Nico Pyrotechnik | Aromatic hydrocarbon modified pyrotechnic smoke compsn. - to produce smoke impenetrable by visible and infrared radiation |
| DE3147850A1 (en) * | 1981-12-03 | 1983-06-09 | Messerschmitt-Bölkow-Blohm GmbH, 8000 München | Wide-band camouflage mist |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4337071C1 (en) * | 1993-10-29 | 1995-03-02 | Nico Pyrotechnik | Pyrotechnic smoke charge for camouflage purposes and its use in a smoke body |
| AU675740B2 (en) * | 1993-10-29 | 1997-02-13 | Nico-Pyrotechnik Hanns-Jurgen Diederichs Gmbh & Co. Kg | Pyrotechnic smoke-generating composition for camouflage purposes and its use in a smoke-generating body |
Also Published As
| Publication number | Publication date |
|---|---|
| NO164591B (en) | 1990-07-16 |
| CA1271334A (en) | 1990-07-10 |
| NO164591C (en) | 1990-10-24 |
| FR2583037A1 (en) | 1986-12-12 |
| FR2583037B1 (en) | 1987-11-13 |
| DE3660487D1 (en) | 1988-09-15 |
| NO861901L (en) | 1986-12-08 |
| EP0210082B1 (en) | 1988-08-10 |
| US4698108A (en) | 1987-10-06 |
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